Zn(II)-catalyzed thiolysis of oxiranes in water under neutral conditions

Thiolysis of a variety of 1,2-epoxides in water at 30 degrees C and pH 7.0 is strongly accelerated by ZnCl(2) (10 mol %) except when amino- and carboxythiophenol are used. The aqueous medium and the catalyst were recovered and reused in various runs without affecting the efficiency of the process.     

Propagation characteristics of pressure disturbances originated by gas jets in fluidized beds

An experimental investigation has been carried out on velocities and amplitudes of pressure disturbances in fluidized beds made of 100–200 μm glass ballotini. Disturbances were originated by gas jetting in a 0.35 m i.d. fluidized bed. A fluidization tube 0.10 m i.d. has also been used. Different types of disturbances have been induced in the bed contained in this tube: injection of a freely rising bubble and of a captive bubble; injection of a bubble chain; and compression of the bed free surface. The dynamic wave character of the disturbances has been shown. Velocities and amplitudes of waves moving through the beds have been measured. In particular, wave velocities have been compared with theoretical results obtained by the application of “pseudo-homogeneous” and “separated phase flow” models.     

Sperner capacities

We determine the asymptotics of the largest family of qualitatively 2-independentk-partitions of ann-set, for everyk>2. We generalize a Sperner-type theorem for 2-partite sets of Körner and Simonyi to thek-partite case. Both results have the feature that the corresponding trivial information-theoretic upper bound is tight. The results follow from a more general Sperner capacity theorem for a family of graphs in the sense of our previous work on Sperner theorems on directed graphs.Work supported in part by the Italian Ministry of the University and of the Scientific Research in the framework of the Algoritmi e Sistemi di Calcolo project.     

Azidolysis of alpha,beta-epoxycarboxylic acids. A water-promoted process efficiently catalyzed by indium trichloride at pH 4.0

The catalytic efficiency of InCl(3), Yb(OTf)(3), and Sc(OTf)(3) in the azidolysis of alpha,beta-epoxycarboxylic acids has been studied in water and in organic solvents, for comparison using NaN(3) and Me(3)SiN(3) as the source of the azido group. In water, the catalytic effectiveness of these metal salts strongly depends on the pH of the aqueous medium and on the type of Lewis acid catalyst. In water their catalytic activity is mostly due to the corresponding aqua ion species, the concentration of which becomes significant when the pH of the aqueous medium is below the corresponding pK(1,1) hydrolysis constant. The process is more efficient in water than in organic solvents. At pH 4.0, InCl(3) is a far better catalyst than Yb(OTf)(3) or Sc(OTf)(3) and allows the highly regio- and diasteroselective preparation of beta-azido-alpha-hydroxycarboxylic acids, which can be isolated in pure form in very high yields.     

Efficient O-trimethylsilylation of alcohols and phenols with trimethylsilyl azide catalyzed by tetrabutylammonium bromide under neat conditions

A very efficient procedure for the trimethylsilylation of a wide variety of alcohols, including primary, allylic, benzylic, secondary, hindered secondary, tertiary, and phenols is reported. The reactions were carried out under neat conditions with trimethylsilyl azide (TMSN(3)) and, when necessary, in the presence of a catalytic amount (20 mol %) of tetrabutylammonium bromide (TBABr) at 30 or 70 degrees C. Under catalytic conditions, the yields of the corresponding trimethylsilyl ethers were greater than 91%. This procedure also allows the selective protection of primary and secondary alcohols in the presence of tertiary ones.     

Finite element error bounds for a curve shrinking with prescribed normal contact to a fixed boundary

We approximate the evolution of a curve subject to motion bycurvature by linear finite elements. The curve evolves insidea given domain and meets orthogonally. We derive optimal boundsfor the error with respect to the L²- and H¹-norms and presentsome computed examples.     

Mode-specific tunneling dynamics in the ground electronic state of tropolone

The mode specificity of proton-transfer dynamics in the ground electronic state (X (1)A(1)) of tropolone has been explored at near-rotational resolution by implementing a fully coherent variant of stimulated emission pumping within the framework of two-color resonant four-wave mixing spectroscopy. Three low-lying (E(vib) approximately 550-750 cm(-1)) vibrational features, assigned to nu(30)(a(1)), nu(32)(b(2)), and nu(31)nu(38)(a(1)), have been interrogated under ambient, bulk-gas conditions, with term energies determined for the symmetric and antisymmetric (tunneling) components of each enabling the attendant tunneling-induced bifurcations of 1.070(9), 0.61(3), and 0.07(2) cm(-1) to be extracted. The dependence of tunneling rate (or hydron migration efficiency) on vibrational motion is discussed in terms of corresponding atomic displacements and permutation-inversion symmetries for the tropolone skeleton.